ACTA CHEMICA SCANDINAVICA 18 (1964) 1099-1104 Mass Spectrometry of Terpenes IIE. Monoterpene Aldehydes and Ketones ERIK von SYDOW ‘Swedish Institute for Food Preservation Research (SIK), Gateborg 16, Sweden ‘Twelve monoterpene aldehydes and ketones wore investigated in a combinod gas clromatogreph-maae spectrometer, mje = Af waa invariably the parent peak. m/e = M—18 was absent or very small for the ketones and cuminic aldehyde, and thus differed from the alcohols and the two acyclic aldehydes investigated. The interpreta- tion of the fragmentation patterns was more difficult than for the hydrocarbons and the aleohols. Mrrterpene hydrocarbons and alcohols have previously been studied in a combined gas chromatograph-mass spectrometer.? The investigations were now extended to include monoterpene aldehydes and ketones, all together twelve compounds. The mass spectra of five ketones have been published by Reed.? The data, presented were, however, neither quite consistent with those obtained in the present study, nor were they as complete, for no information was given on meta-stable ions and besides several mje peaks in the higher regions were missing. EXPERIMENTAL Apparatus, The apparatus and experimental conditions used are described in Part I of this series.’ Although the transfer system between the chromatograph and the mass spectrometer was kept at 200°C no decomposition seemed to have occurred in the com- pounds investigated here. Material. The aldehydes and ketones investigated wero obtained from the following sources: citronellal, geranial and cuminic aldehyde from Haarman & Reimer, Germany, pulegone and fonctions from Fluka AG, Switzerland, carvone, piperitone and campheni- lone from Light & Co., Ltd., England, methone and camphor from Coleman & Bell Co., USA, piperitenone from Dr. ¥.-R. Naves, Givaudan 8. A., Switzerland, and thujone from Dr, ‘t. Norin, Stockholm. ‘The purity of the specimens obtained by separation on the DC column in conjunction with the mass spectrometer in which they were analyzed, was invariably checked by chromatography on polar columns and by infrared spectrophotometry. Acta Chem. Scand. 18 (1964) No. 51100 ERIK VON 8S¥DOW RESULTS AND DISCUSSION ‘The spectra of three monoterpene aldehydes and nine monoterpene ketones are shown in Figs. 1—12. The spectra originally showed peaks at m/e = 18, 28, 82, 40, and 44, originating from H,O (partly), Nz, O,, Ar, and CO, (partly), re- spectively. These peaks have been removed. All compounds investigated had the molecule ion mje = M as parent peak. These together with the three stron- gest peaks above m/e = 67 are given in Table 1 for all compounds investigated. ‘As expected, the general appearance of the spectra did not differ largely from those of the monoterpene alcohols? Table 1. Characteristic peaks in the mass spectra of monoterpene aldehydes and ketones. | Monoterpene | Parent | Base | 2nd strongest 3rd strongest | aldehyde or | peak | peak peak | ketone | | | (above mie = 67)| (above mle = 67) an) ne ee ] ae -| Citronellal ; 18 | 95 | al | Geranial | 52 69 84 94 | | Cuminic aldehyde, 148 133 105 | ws | Menthone | 154 12, 69 | 139 Pulegone 152 81 152 | 109 | Piporitone |e 82 110 i 95 | Carvone 150 82 108 | 93 } | Piperitenone | __150 150 107 135, | ree inet Fi ve | | Thujone 152 al 110 68 | |_Fenchone |? 09,81 | 69, 81 so | | | Caimphenitone | 138 __ 69 138 2 ‘The meta-stable ions observed as diffuse peaks were studied for breakdown patterns. Some meta-stable ions probably remained concealed owing to mask- ing by large ion peaks and the condition of the spectra studied. Generally speaking, the diffuse peaks for the aldehydes and the ketones were less nume- rous and weaker than for the alcohols? and even more so than for the mono- terpene hydrocarbons.t A, Aldehydes. The mass spectra of citronellal, geranial and cuminic aldehyde are presented in Figs. 1—3. No diffuse peaks were observed for these com- pounds, The cracking patterns of the first two were, as expected, quite similar to each other. The base peak is in both cases mje = 69, which fragment is formed by splitting the bond in allylic position to the double bond or bonds present in the molecules. Both citronellal and geranial easily lose one molecule of water thereby giving rise to a monoterpene hydrocarbon ion, from which several characteristic fragments can be deduced in accordance with the known Acta Chem. Scand. 18 (1964) No. 5MASS SPECTRA OF TERPENES III 01 69 CITRONELLAL, | * ne : wf i rs vo wl wats a » a 4g a r jf % rn { \ oR ee em 0 a a em aw Fig, 1. Mass spectrum of citronellal. Fig. 2. Mass spectrum of geranial, breakdown patterns of proper monoterpene hydrocarbons.! The alcohols behave similarily, which is indicated by comparing the spectrum of citronellal with that of geraniol.? The interpretation of the fragmenta m/e = M—43 is not 80 obvious as they may arise by loas of an isopropyl group or a group HCO— CH,—. In the case of cuminic aldehyde (Fig. 3) there seems to be no extra hydrogen atom available for © comparative lose of water on fragmentation a3 mje = M—18 = 130 or fragments derived from this ion are not observed. Oxygen can probably be lost only in the form of the aldehyde group as indi- M—29 cated by mj = 119. This peak might also be explained by loss of CH,—CH,—, but mje = M—29 is not generally so high in mass spectra of non-aldehyde monoterpene compounds. ‘The aromatic aldehyde is obviously 9 = 10 wo "33 | CUMINIC ALDEHYDE 2 ‘0 n woe soe aol = af 2 fH A ow Gt komo Mo ws | 82 wa Oo no oo Fig. 3, Mass spectrum of cuminic aldehyde. Fig. 4. Mass spectrum of methone. Acta Chem. Scand. 18 (1964) No. 51102, ERIK VON SYDOW more stable than the acyclic ones, as revealed by the presence of higher con- centrations of ions with large m/e-values. The three or possibly four strongest peaks correspond to fragments containing the aldehyde group indicating the firmness with which it is bound to the aromatic ring. m/e = 91 is a common peak in mass spectra of alkylated aromatic compounds. It has been inter- preted as the tropylium ion (C,H,*).* B. Monocyclic ketones. The mass spoctra of menthone, pulegone, piperitone, carvone and piperitenone are shown in Figs. 4—8. S = a on 4 z 2 eal wo} E i i al 4 oj 2 2a) wo} oR oh mmo 0 wo Bg ew co wo, mo Fig. 5. Mass spectrum of pulegono. Fig. 6. Mass spectrum of piperitone. The ketones differ from the aldehydes and the alcohols in that their mass spectra show a very small or no peak at m/e — M—18, corresponding to loss of one water molecule from the parent molecule. This difference is very helpful 109 iw 0 oo PIPERITENONE, 1 intensity % oe ao fo ao oto Mo wo OO OO Wo" tho” to" 160 Fig. 7. Maes spectrum of earvone. Fig. 8. Mass spectrum of piperitenone. Acta Chem. Scand. 18 (1964) No. 5MASS SPECTRA OF TERPENES IL 1103 in the investigation of structures of unknown compounds. Interpretation of the fragmentation patterns of the compounds of this group is very difficult, as very few diffuse peaks were observed. Besides there is another difficulty in that the mass numbers of the fragments C = O and CH,—CH, are both 28. Menthone showed one diffuse peak at 63.0 corresponding to the possible break- down reaction 112+ + 84+ + 28, but it is not possible to attribute definite structures to any of these three fragments. The spectrum of carvone had diffuse peaks at 35.4 and 89.2 corresponding to 82+ + 54+ + 28 and 93+ + 91+ + 2, respectively. Piperitenone has a spectrum quite different from the other mono- cyclic ketones investigated. The parent peak is also tho base peak, mje = M, which means that this moleoule is more stable than the others, probably owing to the conjugated double bond system present. Three diffuse peaks were ro 10 so Fy “THUJONE, ‘CAMPROR ts 105 * 1 ms me I oF $ og ) so E mwise st 2 ap aot wise xf & wt & a x c " oe" to” Go 90,0 100 to” so” wo 0 "0 40 6.80 wo mo mo wo Fig. 9. Mass spectrum of camphor. Fig. 10. Mess spectrum of thujono. " FENCHONE ‘I ~ ae nl # 1 2 5 ae soe = ao a a c i & ay 34 W} wg Sil | | ote a co ag a Ho to” Wo oO Gay he toe Fig. 11. Mass spectrum of fenchone. ‘Fig. 12, Mass spectrum of camphenilone. Acta Chem. Scand. 18 (1964) No. 510s ERIK VON 8YDOW Table 2. Meta-stable ions of fenchons. | Diffuse | Possible break-down 1 | | os — | | v1 | 152+ + 109+ + 43 | | m1 | silts mt 4 2 63.1 137+ 93+ 4 44 | | 36.7 123+ + 67+ 4 56 82+ 5 85+ 4 27 | 34.5 137+ 5 69+ + 68 | 81 > 53+ + 28 24,3 6ot + 41+ + 28 Note,* m 1» where m, and m, are the masses of the original and the generated ions, res pectively, giving tise to a diffuse peak at *m. observed, namely at 84.8, 77.3, and 58.4. They may be interproted as arising ing to the following scheme 1354, -> 107, + 28, 107+ » 91* + 16 and 107 g-> 79* + 28. ©. Bicyclic ketones. The mass spectra of camphor, thujone, fenchone and camphenilone are given in Figs. 9—12. As for the monocyclic ketones m/e = ‘M-18 is missing or very weak in these spectra. The spectrum of camphor revealed one diffuse peak at 76.8 corresponding to the breakdown reaction 152 +-+ 108+ + 44. Quite a few meta-stable ions formed were observed in the mass spectrum of fenchone (Table 2), while none were observed in the spectra of the two other compounds investigated. ‘The mass spectra of monoterpene ketories frequently show the presence of the ion m/e = M—42 or M—44, while the spectra of the hydrocarbons and the alcohols generally have peaks at m/e = M—43, corresponding to a loss of an isopropyl group, or at mje-values derived from this fragment. It therefore seems likely that the loss of 42 or 44 units from the ketones does not correspond to a loss of an isopropyl group but rather to an oxygen-containing fragment. Acl int, I feel indebted to Dr. R. Ryhage for placing the combined gas chromat ‘mass spectrometer with technical assistanco to my disposal, and to thoso, mentic Wve, who courteously supplied me with specimens of monoterpene aldehydes and ketone: REFERENCES 1, Ryhago, R. and von Sydow, E, Acta Chem. Scand. 17 (1963) 2025. 2. von Sydow, E. Acta Chem. Scand. 17 (1963) 2504. 3. Reed, R. J. Mass Spectra of Terpenes. Chapter 13 of McLafferty, F. W. (Ed.) Mass Spectrometry of Organic Ions, Now York 1963. 4. Rylander, P. N., Meyerson, 8. and Grubb, H. M. J. Am. Chem. Soc. 79 (1957) 842. Received March 10, 1964. Acta Chem. Scand. 18 (1964) No. 5